Geochemistry of Southern Ocean sediments

Reconstructing past detrital flux and provenance in the Southern Ocean provides information about changes in source regions associated with climate variations and transport pathways. We present a Last Glacial Maximum (LGM) to Holocene comparison of 230Th normalised fluxes combined with sediment provenance data (Pb, Nd and Sr isotopes) from a latitudinal core transect in the eastern Atlantic sector of the Southern Ocean (ODP Leg 177 cores). We compare the radiogenic isotopic composition (IC) of detritus in these cores to that of cores proximal to potential source areas. We observe a well-defined latitudinal Holocene gradient in both detrital flux and provenance of sediment. High detrital fluxes in the north are associated with terrigenous material derived from southern Africa, while low detrital fluxes in the south are associated with supply from southern South America, West Antarctica and the South Sandwich Islands. The data suggest that this well-defined Holocene gradient in detrital flux and sediment provenance is controlled by the flow of the Antarctic Circumpolar Current (ACC) and the position of its frontal zones. The LGM is characterised by 2 to 6 times higher than modern detrital fluxes at most ODP Leg 177 sites. The LGM detrital fluxes do not show a latitudinal trend and suggest a greater supply of glaciogenic detritus sourced from southern South America. Glacial Patagonian outwash sediments (< 5 µm fraction) were analysed and compared to the bulk compositions of the marine sediments. The Pb IC of the Patagonian sediments is very similar to the glacial IC of sediments in the Scotia Sea and at ~ 49° S latitude in the eastern Atlantic sector. We propose that the glacial IC of sediments is controlled by increased delivery of Patagonian detritus initially supplied by glaciers and then transported at depth via the ACC.

Raw X-ray fluorescence (XRF) scannings and radiocarbon age of sediment cores GeoB8331-4, and GeoB8322-2

Variations in the sediment input to the Namaqualand mudbelt during the Holocene are assessed using an integrative terrestrial to marine, source to sink approach. Geochemical and Sr and Nd isotopic signatures are used to distinguish fluvial sediment source areas. Relative to the sediments of the Olifants River, craton outcrops in the northern Orange River catchment have a more radiogenic Sr and a more unradiogenic Nd isotopic signature. Furthermore, upper Orange River sediments are rich in heavier elements such as Ti and Fe derived from the chemical weathering of Drakensberg flood basalt. Suspension load signatures change along the Orange River's westward transit as northern catchments contribute physical weathering products from the Fish and Molopo River catchment area. Marine cores offshore of the Olifants (GeoB8323-2) and Orange (GeoB8331-4) River mouths show pulses of increased contribution of Olifants River and upper Orange River input, respectively. These pulses coincide with intervals of increased terrestrial organic matter flux and increased paleo-production at the respective core sites. We attribute this to an increase in fluvial activity and vegetation cover in the adjacent catchments during more humid climate conditions. The contrast in the timing of these wet phases in the catchment areas reflects the bipolar behavior of the South African summer and winter rainfall zones. While rainfall in the Orange River catchment is related to southward shifts in the ICTZ, rainfall in the Olifants catchment is linked to northward shifts in Southern Hemisphere Westerly storm tracks. The later may also have increased southern Benguela upwelling in the past by reducing the shedding of Agulhas eddies into the Atlantic. The high-resolution records of latitudinal shifts in these atmospheric circulation systems correspond to late Holocene centennial-millennial scale climate variability evident in Antarctic ice core records. The mudbelt cores indicate that phases of high summer rainfall zone and low winter rainfall zone humidity (at ca. 2.8 and 1 ka BP) may be synchronous with Antarctic warming events. On the other hand, dry conditions in the summer rainfall zone along with wet conditions in the winter rainfall zone (at ca 3.3, 2 and 0.5 ka BP) may be associated with Antarctic cooling events.

(Table S1) Age determination of Atlantic Ocean sediment cores

Well-dated benthic foraminifer oxygen isotopic records (d18O) from different water depths and locations within the Atlantic Ocean exhibit distinct patterns and significant differences in timing over the last deglaciation. This has two implications: on the one hand, it confirms that benthic d18O cannot be used as a global correlation tool with millennial-scale precision, but on the other hand, the combination of benthic isotopic records with independent dating provides a wealth of information on past circulation changes. Comparing new South Atlantic benthic isotopic data with published benthic isotopic records, we show that (1) circulation changes first affected benthic d18O in the 1000-2200 m range, with marked decreases in benthic d18O taking place at ~17.5 cal. kyr B.P. (ka) due to the southward propagation of brine waters generated in the Nordic Seas during Heinrich Stadial 1 (HS1) cold period; (2) the arrival of d18O-depleted deglacial meltwater took place later at deeper North Atlantic sites; (3) hydrographic changes recorded in North Atlantic cores below 3000 m during HS1 do not correspond to simple alternations between northern- and southern-sourced water but likely reflect instead the incursion of brine-generated deep water of northern as well as southern origin; and (4) South Atlantic waters at ~44°S and ~3800 m depth remained isolated from better-ventilated northern-sourced water masses until after the resumption of North Atlantic Deep Water (NADW) formation at the onset of the Bølling-Allerod, which led to the propagation of NADW into the South Atlantic.

Detrital layer thickness in 12 varved sediment cores in Lake Mondsee and related flood events AD1976-2005

A succession of 23 sub-millimetre to maximum 12-mm-thick, mostly flood-triggered detrital layers, deposited between 1976 and 2005, was analysed in 12 varved surface sediment cores from meso-scale peri-alpine Lake Mondsee applying microfacies and high-resolution micro X-ray fluorescence analyses. Detailed intrabasin comparison of these layers enabled identification of (i) different source areas of detrital sediments, (ii) flood-triggered sediment flux and local erosion events, and (iii) seasonal differences of suspended flood sediment distribution within the lake basin. Additional calibration of the detrital layer record with river discharge and precipitation data reveals different empirical thresholds for flood layer deposition for different parts of the basin. At proximal locations detrital layer deposition requires floods exceeding a daily discharge of 40 m**3/s, whereas at a location 2 km more distal an hourly discharge of 80 m**3/s and at least 2 days of discharge above 40 m**3/s are necessary. Furthermore, we observe a better correlation between layer thickness and flood amplitude in the depocentre than in distal and proximal areas of the basin. Although our results are partly site-specific, the applied dual calibration approach is suitable to precisely decipher flood layer formation processes and, thereby, improve the interpretation of long flood time series from lake sediments.

Pre-glacial to glacial sediment thickness grids for the Southern Pacific Margin of West Antarctica, NetCDF files

Circum-Antarctic sediment thickness grids provide constraints for basin evolution and paleotopographic reconstructions, which are important for paleo-ice sheet formation histories. By compiling old and new seismic data, we identify sequences representing pre-glacial, transitional and full glacial deposition processes along the Pacific margin of West Antarctica. The pre-glacial sediment grid depicts 1.3 to 4.0 km thick depocenters, relatively evenly distributed along the margin. The depocenters change markedly in the transitional phase at, or after, the Eocene/Oligocene boundary, when the first major ice sheets reached the shelf. Full glacial sequences, starting in the middle Miocene, indicate new depocenter formation North of the Amundsen Sea Embayment and localized eastward shifts in the Bellingshausen Sea and Antarctic Peninsula basins. Using present-day drainage paths and source areas on the continent, our calculations indicate an estimated observed total sedimentary volume of ~10 x 10**6 km**3 was eroded from West Antarctica since the separation of New Zealand in the Late Cretaceous. Of this 4.9 x 10**6 km**3 predates the onset of glaciation and need to be considered for a paleotopography reconstruction of 34 Ma. Whereas 5.1 x 10**6 km**3 postdate the onset of glaciation, of which 2.5 x 10**6 km**3 were deposited in post mid-Miocene full glacial conditions.

(Table 1) Clay and non-clay mineral composition of dirty ice samples from across the Arctic

Extensive dirty ice patches with up to 7 kg/m**2 sediment concentrations in layers of up to 10 cm thickness were encountered in 2005 and 2007 in numerous areas across the central Arctic. The Fe grain fingerprint determination of sources for these sampled dirty ice floes indicated both Russian and Canadian sources, with the latter dominating. The presence of benthic shells and sea weeds along with thick layers (2-10 cm) of sediment covering 5-10 m2 indicates an anchor ice entrainment origin as opposed to suspension freezing for some of these floes. The anchor ice origin might explain the dominance of Canadian sources where only narrow flaw leads occur that would not favor suspension freezing as an entrainment process. Expandable clays, commonly used as an indicator of a Kara Sea origin for dirty sea ice, are present in moderately high percentages (>20%) in many circum-Arctic source areas, including the Arctic coasts of North America. Some differences between the Russian and the North American coastal areas are found in clay mineral abundance, primarily the much higher abundance of chlorite in North America and the northern Barents Sea as opposed to the rest of the Russian Arctic. However, sea ice clay mineralogy matched many source areas, making it difficult to use as a provenance tool by itself. The bulk mineralogy (clay and non-clay) does not match specific sources possibly due to reworking of the sediment in dirty floes through summer melting or the failure to characterize all possible source areas.

Hydrogen isotope compositions of terrestrial plant-wax n-alkanes analysed on a transect of marine surface sediment samples from 1°N to 28°S off southwest Africa

A transect of marine surface sediment samples from 1° N to 28° S off southwest Africa was analysed to verify the application of hydrogen isotope compositions of terrestrial plant-wax n-alkanes preserved in ocean sediments as a proxy for continental hydrological conditions. Conditions on the adjacent continent range from humid evergreen forests to deciduous forests, wood- and shrub land and further to arid grasslands and deserts. The hydrogen isotope values for the dominant n-alkane homologues (C29, C31 and C33) vary from -123 per mil to -141 per mil VSMOW and correlate with the modelled hydrogen isotope composition of mean annual and growing season precipitation of postulated continental source areas (r up to 0.8, p < 0.01). The apparent hydrogen isotope fractionation between alkanes and mean annual precipitation is remarkably uniform (-109 per mil on average, Sigma <= 5 per mil, n = 27). Potentially, effects of aridity on the apparent hydrogen isotope fractionation are concealed by the contribution of different plants (C3 dicotyledons vs C4 grasses). Thus, isotope ratios of leaf wax n-alkanes preserved in ocean margin sediments in these and similar tropical regions may be directly converted to dD ratios of ancient precipitation by employing a constant hydrogen isotope fractionation.

Kaolinite/Chlorite ratio of sediment core GeoTü SL143

The ratio between the clay minerals kaolinite and chlorite has been investigated in high resolution in a late Quaternary sediment core from the central Aegean Sea. The record spans the last ca. 105 ka. The kaolinite/chlorite ratio was used to reconstruct the fine-grained aeolian dust influx from the North African deserts, mainly derived from desiccated lake depressions. It therewith can be used as a proxy for wind activity, aridity and vegetation cover in the source area. The data document three major humid phases in North Africa bracketing the formation of sapropel layers S4, S3 and S1. They occur at >105-95 ka, 83.5-72 ka and 14-2 ka. The first two phases are characterised by relatively abrupt lower and upper boundaries suggesting a non-linear response of vegetation to precipitation, with critical hydrological thresholds. In contrast, the onset and termination of the last humid period were more gradual. Highest kaolinite/chlorite ratios indicating strongest aeolian transport and aridity occur during Marine Isotope Stage (MIS) 5b, at ca. 95-84 ka. The long-term decrease in kaolinite/chlorite ratios during the last glacial period indicates a gradual decline of deflatable lake sediments in the source areas.

Geochemistry of ODP Hole 108-658C sediments

During the African Humid Period (AHP), much of the modern hyperarid Saharan desert was vegetated and covered with numerous lakes. In marine sediments off northwestern Africa, the AHP is represented by markedly reduced siliciclastic sediment flux between ~ 12.3 and 5.5 ka. Changes in the origin of this terrigenous sediment fraction can be constrained by sediment chemistry and radiogenic isotope tracers. At Ocean Drilling Program (ODP) Site 658, Hole C (20°44.95'N, 18°34.85'W, 2263 mbsl), the neodymium (Nd) isotope composition of terrigenous detritus shows little variability throughout the last 25 kyr, indicating that the contributing geological terranes have not changed appreciably since the last glacial period. In contrast, there were large and abrupt changes in strontium (Sr) isotope ratios and chemical compositions associated with the AHP, during which 87Sr/86Sr ratios were markedly less radiogenic, and sediments show higher chemical indices of alteration. We show that sediment geochemical changes during the AHP cannot be attributed to changes in the source terranes, physical sorting, or intensity of chemical weathering. The low 87Sr/86Sr and high Sr concentrations of AHP-age samples also conflict with the interpretation of increased fine-grained, fluvially derived sediments. We propose that the most significant compositional changes at ODP 658C are due to the addition of an aluminosilicate component that has a highly altered major element signature but is enriched in soluble elements like Sr and magnesium (Mg) compared to aluminum (Al) and has low 87Sr/86Sr relative to local terrigenous source areas. We interpret these characteristics to reflect authigenic sediment supply from extensive North African paleolake basins that were prevalent during the AHP.

(Appendix A) Oxygen and carbon isotope results of detrital carbonate grains of Heinrich layers from HU90-013-028 and IODP Sites 303-U1302/U1303/U1308 in the North Atlantic Ocean

We report oxygen and carbon isotope results of detrital carbonate grains from Heinrich layers at three sites in the North Atlantic located along a transect from the Labrador Sea to the eastern North Atlantic. Oxygen isotopic values of individual detrital carbonate grains from six Heinrich layers at all sites average - 5.6 ppm ± 1.5 ppm (1sigma; n = 166), reflecting values of dolomitic limestone derived from source areas in northeastern Canada. The d18O of bulk carbonate at Integrated Ocean Drilling Program (IODP) Site U1308 (re-occupation of Deep Sea Drilling Project (DSDP) Site 609) in the eastern North Atlantic records the proportion of detrital to biogenic carbonate and d18O decreases to - 5 ppm during Heinrich (H) events 1, 2, 4 and 5 relative to a background value of ~ 1 to 2 ppm for biogenic carbonate. Bulk d18O also decreases during H3 and H6 but only attains values of - 1ppm, indicating either a greater proportion of biogenic-to-detrital carbonate or a different source. Because the d18O of detrital carbonate is ~ 9 ppm lower than foraminifer carbonate, any fine-grained detrital carbonate not removed from the inner test chambers will lower foraminifer d18O. We conclude bulk carbonate d18O is a sensitive proxy for detrital carbonate and may be useful for identifying Heinrich layers in cores within and near the margins of the North Atlantic ice-rafted detritus (IRD) belt.

Pollen analysis of sediment core GeoB1023-5

A high resolution marine pollen record from site GeoB1023, west of the northern Namib desert provides data on vegetation and climate change for the last 21 ka at an average resolution of 185 y. Pollen and spores are mainly delivered to the site by the Cunene river and by surface and mid-tropospheric wind systems. The main pollen source areas are located between 13°S and 21°S, which includes the northern Namib desert and semi-desert, the Angola-northern Namibian highland, and the north-western Kalahari. The pollen spectra reflect environmental changes in the region. The last glacial maximum (LGM) was characterised by colder and more arid conditions than at present, when a vegetation with temperate elements such as Asteroideae, Ericaceae, and Restionaceae grew north of 21°S. At 17.5 ka cal. B.P., an amelioration both in temperature and humidity terminated the LGM but, in the northern Kalahari, mean annual rainfall in the interval 17.5-14.4 ka cal. B.P. was probably 100-150 mm lower than at present (400-500 mm/y). The Late-glacial to early Holocene transition includes two arid periods, i.e. 14.4-12.5 and 10.9-9.3 ka cal. B.P. The last part of the former period may be correlated with the Younger Dryas. The warmest and most humid period in the Holocene occurred between 6.3 and 4.8 ka cal. B.P. During the last 2000 years, human impact, as reflected by indications of deforestation, enhanced burning and overgrazing, progressively intensified.

Late Pleistocene sedimentation in the Western Mediterranean Sea

Sediment cores from the Western Mediterranean Sea (WMS) have been analyzed for their bulk element composition, delta18O values of planktic foraminiferal tests, and 87Sr/86Sr and 143Nd/144Nd ratios of their bulk lithogenic components. The investigated time interval comprises the last 215 kyr. Si/Al and Ti/Al ratios as well as radiogenic isotope compositions indicate changes in the provenance of the lithogenic components between glacial intervals and interglacial phases. Comparison with modern data indicates that detrital input from the northwestern and northeastern Sahara may have dominated during interglacial phases. In contrast, during glacial periods the accumulation rate of terrigenous sediment is high and changes in the sediment source areas are evident that may be related to changes in the prevailing atmospheric circulation over the basin and its source areas. A productivity reconstruction based on bio-mediated barium accumulation rates reveals increased surface productivity during glacial phases. Intervals time-equivalent to sapropel formation in the Eastern Mediterranean Sea (EMS) show no changes in surface productivity compared to the intervening intervals. Comparison of the productivity patterns between the WMS and EMS suggests a decoupling during Late Pleistocene sapropel formation and highlights the importance of more localized factors such as the freshwater drainage basin.

Physical oceanography from CTD during Maria S. Merian cruise MSM20/4 in spring 2012

With an extension of > 40 km**2 the recently discovered Campeche cold-water coral province located at the northeastern rim of the Campeche Bank in the southern Gulf of Mexico belongs to the largest coherent cold-water coral areas discovered so far. The Campeche province consists of numerous 20-40 m-high elongated coral mounds that are developed in intermediate water depths of 500 to 600 m. The mounds are colonized by a vivid cold-water coral ecosystem that covers the upper flanks and summits. The rich coral community is dominated by the framework-building Scleractinia Enallopsammia profunda and Lophelia pertusa, while the associated benthic megafauna shows a rather scarce occurrence. The recent environmental setting is characterized by a high surface water production caused by a local upwelling center and a dynamic bottom-water regime comprising vigorous bottom currents, obvious temporal variability, and strong density contrasts, which all together provide optimal conditions for the growth of cold-water corals. This setting - potentially supported by the diel vertical migration of zooplankton in the Campeche area - controls the delivering of food particles to the corals. The Campeche cold-water coral province is, thus, an excellent example highlighting the importance of the oceanographic setting in securing the food supply for the development of large and vivid cold-water coral ecosystems.

Characteristics of light and dark alternations in Owen Ridge sediments (Appendix)

Clay mineral relative abundances in approximately 450 samples from cores recovered during ODP Leg 117 in the Arabian Sea have been used to examine the paleoclimatic, paleoenvironmental, and tectonic histories of the Indus Fan, Owen Ridge, Oman margin, and adjacent continental source regions. Geographic variations in the relative abundances of minerals and correlations with depositional processes support previous interpretations that smectite has been supplied from weathering of the Deccan Traps; illite and chlorite have been supplied either from the Himalayas via marine transport or from the Iran-Makran region by winds; and palygorskite has been supplied from the Arabian peninsula and Somalia by winds. Pleistocene sediments of the Indus Fan record two modes of deposition: turbidites supplied from the Indus drainage and dominated by illite and chlorite, and pelagic carbonates containing smectites and wind-transported palygorskite. Local and regional causes for shifts between these depositional processes cannot be demonstrated conclusively with the data available, but sea-level fluctuations probably exerted a significant control on the rate of turbidite influx. Lower Miocene sediments on the Owen Ridge are also turbidites supplied by the Indus drainage; in the middle Miocene, a shift to pelagic carbonates records the uplift of the Owen Ridge, and is accompanied by the increased relative importance of wind-transported palygorskite. Associations of palygorskite and biosiliceous components in middle to upper Miocene sediments are interpreted to record vigorous monsoonal circulation and accompanying upwelling-produced biological productivity. Mineralogic and geochemical data indicate that light/dark color alternations in upper Miocene sediments on the Owen Ridge record climatic fluctuations, but the climatic significance of similar alternations in Pliocene-Pleistocene sediments is unclear. Palygorskite is the dominant clay on the Oman margin, reflecting proximity to its source areas. On the Oman margin, clay mineral relative abundances are most variable at structurally complex sites, indicating that local depositional settings have been influenced by their tectonic histories since the Miocene.

Distribution of heavy minerals in sediment cores from the Laptev Sea continental margin and the central Arctic Ocean

Focussing on heavy-mineral associations in the Laptev-Sea continental margin area and the eastern Arctic Ocean, 129 surface sediment samples, two short and four long gravity cores have been studied. By means of the accessory components, heavy-mineral associations of surface sediment samples from the Laptev-See continental slope allowed the distinction into two different mineralogical provinces, each influenced by fluvial input of the Siberian river Systems. Transport pathways via sea ice from the shallow shelf areas into the Arctic Ocean up to the final ablation areas of the Fram Strait can be reconstructed by heavy-mineral data of surface sediments from the central Arctic Ocean. The shallow shelf of the Laptev Sea seems to be the most important source area for terrigenous material, as indicated by the abundant occurence of amphiboles and clinopyroxenes. Underneath the mixing Zone of the two dominating surface circulation Systems, the Beaufort- Gyre and Transpolar-Drift system, the imprint of the Amerasian shelf regions up to the Fram Strait is detectable because of a characteristical heavy-mineral association dominated by detrital carbonate and opaque minerals. Based On heavy-mineral characteristics of the potential circum-Arctic source areas, sea-ice drift, origin and distribution of ice-rafted material can be reconstructed during the past climatic cycles. Different factors controlling the transport of terrigenous material into the Arctic Ocean. The entrainment of particulate matter is triggered by the sea level, which flooded during highs and lows different regions resulting in the incorporation of sediment from different source areas into the sea ice. Additionally, the fluvial input even at low stands of sea level is responsible for the delivery of material of distinct sources for entrainment into the sea ice. Glacials and interglacials of climate cycles of the last 780 000 years left a characteristical signal in the central Arctic Ocean sediments caused by the ice- rafted material from different sources in the circum-Arctic regions and its change through time. Changes in the heavy-mineral association from an amphibole-dominated into a garnet-epidote-assemblage can be related to climate-related changes in source areas and directions of geostrophic winds, the dominating drive of the sea-ice drift. During Marine Isotope Stage (MIS) 6, the central Arctic Ocean is marked by an heavy-mineral signal, which occurs in recent sediments of the eastern Kara Sea. Its characteristics are high amounts of epidote, garnet and apatite. On the other hand, during the Same time interval a continuous record of Laptev Sea sediments is documented with high contents of amphiboles on the Lomonosov Ridge near the Laptev Sea continental slope. A nearly similar Pattern was detected in MIS 5 and 4. Small-scale glaciations in the Putorana-mountains and the Anabar-shield may have caused changes in the drainage area of the rivers and therefore a change in fluvial input. During MIS 3, the heavy-mineral association of central Arctic sediments show similar patterns than the Holocene mineral assemblage which consists of amphiboles, ortho- and clinopyroxenes with a Laptev Sea source. These minerals are indicating a stable Transpolar-Drift system similar to recent conditions. An extended influence of the Beaufort Gyre is only recognized, when sediment material from the Amerasian shelf areas reached the core location PS2757-718 during Termination Ib. Based On heavy-mineral data from Laptev-Sea continental slope Core PS2458-4 the paleo-sea-ice drift in the Laptev Sea during 14.000 years was reconstructed. During Holocene sea-level rise, the bathymetrically deeper parts of the Western shelf were flooded first. At the beginning of the Atlantic stage, nearly the entire shelf was marine influenced by fully marine conditions and the recent surface circulation was established.